Drying oil composition



I atented May 12,

UNITED STATES DRYING our COMPOSITION Robert D. Bonney,. Glen Ridge, and Walter B.

Em. West Orange, N. L, assignors' to 0021- golenm Nairn Inc., a. corporation of New York no Drawing. Application June so, 1934,

Serial No. 733,306

22 Claims.

'10 oxidized drying or semi-drying oils with select! ed fatty acids.

We have discovered that when drying or semidrying oils are subjected to oxidation limited substantially tothe formation of uncoagulated products of oxidation and such products of oxidation are further treated to effect a separation therefrom -of a substantial proportion. of the unoxidized and non-hardening constituents, we obtain products of remarkable properties, particularly adapted for use in protective coating compositions and in binders for mouldable compositions of various sorts, such as linoleum. This subject matter is disclosed and claimed in our co-pending application Serial No. 773,305, filed June 30, 1934; and. Serial No. 576,206, filedNov. 19, 1931, which on July 31, 1934 matured into Patent .No.

1,968,244. -W e have now further discovered that if this oxidized 011 product, separated from a substantial proportion of unoxidized and non-hardening constituents, is caused to react with selected fatty. acids of either thesaturated or unsaturated series, there are obtained new resinlike substances which are even more valuable in many respects for use as or in the vehicle for enamels, paints, varnishes, and similar protective coatiugcompositions and also in or as the binder for mouldable compositions. We have still further discovered that such novel resin-like products mayalso be obtained by subjecting a drying or semi-drying .oil to an oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, simultaneously or subsequently causing interaction of the prod- Broadly, our process invention, whereby the ucts of oxidation with selected fatty acids, and

novel resin-like substances of our product lnven- I tion maybe obtained, comprises the steps of sub- Jecting a substance which contains adrylng or semi-drying oil to an oxidizing treatment limited substantially to the formation of 'uncoagulated 5 products of oxidation, simultaneously orv subsequently causing interaction between certain constituents'of the products of the oil oxidation and a fatty acidfor fatty acids selected from that group or series of fatty acids characterized by 14 0 to 22 carbon atoms, and before orsubsequent to such interaction of the fatty acids with constituents of the oxidized oil, treating such oil oxidation products, or the reaction products thereof' with the fatty acid or acids, to remove therefrom 15 a substantial proportion of the unoxidized oil constituents and non-hardening constituents. Our product invention contemplates certain new resin-like substances composed essentially of the r I reaction products of fluid oxidized glycerides of linoleic and linolenic acids which result from the oxidation of drying or semi-drying oils, withiree fatty acids of 14 to 22 carbon atoms, suchreaction products being separated from a substantial proportion of the unoxidized and non-hardening oil constituents of the product of the oil oxidation.

In preparing the novel products ofour invention we prefer to employ linseed oil as the base. Other drying or semi-drying oils-such as perlila oil,.rubber. seed oil, or soya bean-oil may be used and, in general, any drying or semi-drying oil which, upon oxidation, yields a substantial amount of the oxidized glycerides of linoleic and/or linolenic acids in fluid phase will befound satisfactory. I I 3 The fatty acids which, according to our invention are combined with the oxidized but'uncoagulated glycerides of linoleic and/or. linol'enic acids resulting from the oxidation treatment of the dryingor semi-drying oil, may comprise both those designated as unsaturated fatty acids and those known as saturated and hydroxy saturated fatty acids. For the purposes of our invention, however, we propose to employ fattyacids 4 selected from that group which includes the sev-I eral fatty acid series characterized by 14 to 22 carbon atoms. Such group includes unsaturated fatty acids of the oleic acid series, CuHm-zOz of which oleic acid CraHuOa and tetradecylenic acid so 'tracting solvent. The

' cludes saturated fatty m CrsHscO: are typical some 2 a i CuHaOI are typical examples; the llnoleic acid series Cums-40:, of which linoleic acid CnHaaOs is" a typical example; the llnolenic acid series Calla-40 f which linolenic acid CnHacOz is a typical example; and the clupanodonic acid series CnHm-r o0z, of which clupanodonie acid CnHuOa is a typical example. The group also in- I acids of the series CnHnlOr of which palmitic acid Cannon and stearic acid examples as well as the hydroxy unsaturated fatty acid CnHnMOs of which ricinoleic acid'CnHn(OH)COOH is a typical ex-' ample.- The selection of the particular fatty acid or mixture of fatty acids will'of course be governed by the particular properties which are desired in the ultimate product as hereinafter more fully set forth. The amount fatty acid which is oil constituents may vary will substantially exceed'the amount normally found in drying or semi-drying oils. we prefer to limit the amount to somewhat less than the calculated reacting equivalent (based on the amount of the oxidized glycerides of linoleic and linolenic acids present in the prepared oil component) so that there will be a minimum of free fatty acid p resent in the ultimate reaction products: In

general we propose to eombinewith the desired oxidized but uncoagulated glycerides ofthe' dryorsemidrying oil to 25%,, y weight, of fatty Y r The process of ourinvention may be practiced in several waysdepending upon the sequence of the several'essential stepsthereof above recited. By way of illustrating, various aspects of our in- .vention we will describe in detail several alternasum-s0 to 155 and about a to-4 thereof 1% one volume'of the oxidized oil should the procedures in accordance therewith.

HefhOdI The method involves first, the lim- .ited oxidation of the drying or semi-drying oil,

second, the's'eparation from the productsof oxida-' tion of a substantial proportion of unoxidized oil constituents and non-hardening oil constituents, selected fatty acids withthe oxidized and treated oil which be heldin solution in a solvent.-

Example-Linseed oil is heated'to oboutsoi c.

and a suitable drier; for instance, 94% cobalt linolea'te, is added. The. oilat'a temperature ofrapproximately 80" C. is then blownwith air or is aerated with an equivalent oxygen containing gas for to 25 hours. when a tested sample Just fails to completely dissolve in ethyl ether, oxidation is discontinued. The batch is then cooled and treated to effect a separation of the unoxidlzed andnonhardening oil cons tuents. This separation may be effected by subjecting the oxidized oil to selective extraction with a-solvent' capable of dissolving the undesirable constituents butpossessing little, if any, solvating action upon the oxidized but 'uncoagulat d slvcerldesor linolenic and linoleic acids which are desirable as the oil base .for the. novel. resinous products of .ourinvention.

preferred solvent is petroleum ether (boiling volumes be glllployed. Petroleum naphtha (boiling range used as an equivalent exoiddized but uncoa ated constitutents of the oil which are desirable constituents for the preparation of the novel reaction products of our invention form a lower layer other similar water and proportion of vide a 60% to 80% solution. combined with the within wide limits but I preferablydissolved in a suitable solvent, such as toluol, xylene, iii-flash coal 'tar'naphtha, or any immiscible solvent, to pro- To this solution of the desired oxidized but uncoaguiated constituents of the drying or semidrying oil, separated from a substantial proportion of the unoxidized and non-hardening oil con-- 4 obtained by the oxidizing and separating treatment above described are stituents" of the product of the oil oxidation, is

added a fatty acid or a selectedfrom that group above described and characterized by 14 to 22 carbon atoms. Continuing the typical illustrative example, to 8 parts by weight of the oxidized and treated linseed oil, dissolved in toluol to form a 60% solution, is added 1 part by weight of the mixed fattyacids of linlinoleic and linolenic' This mixture is refluxed for ,45 min-- seed oil, comprisingchiefly fatty acids. utes'in a standard type of refluxing, unit equipped with acondenser designed to trap .out anycone, densed water liberated byzthe reaction and prevent its return to the reactioncharnber.

mixture of fattyacids I resinous product resulting from the refluxing op eration, either in solution or freed of solvent,

constitutes one embodiment of ,ourproduct invention.- r w a The refluxing operation may beeflected with orswithoutthe aid of a catalytic agentr, Among the catalysts that-may num chloride, hydrogen chloride and lactic acid, any one of whichwill facilitate reaction. The amount of catalyst maybe varied but, ingeneral, an amounteq'ual to50.l to 1% byweightof the beemployed are alumitotal'solids in the reaction chamber will be found satisfactory.

' Method 11 The second method comprises, firstjoxidizing the drying or semi-drying oil while limiting such oxidation to the formation of uncoagulatedproducts of oxidation, second, refluxing suchil 'oducts of oxidation with selected fatty v acids in the presence of a common solvent, and finally, treating the reaction'products obtained by the] refluxing operation to separate therefrom a substantial proportion of'the'unoxidized and non-hardening oil constituents. 1 Emmple.'-Perilla oil is heated to about'80 C. and a suitable drier such as .02% vofcobalt naphthenate is added. Q'I'he. oilat approximately, 80 C. is then' blown with air for 10 to 25 hours.

When a tested sample just fails; todissolvein 1 ethyl ether the oxidation is discontinued. To 10 parts by weightof this oxidized: oil, dissolved in toluol 'or otherequlvalent solvent, to forms solution, is'added' 1' part :by weight of palmltic acid and 1 part of stearic acid. This mixture is then refluxed for one" hour in a standard type of refluxing unit equipped rwit'h a condenser designed to trap out any condensed water; liberated by the reaction'and preventgits returnto the reaction chamber. A small amount of hydrochloric acid (0.1% by weight) may be used if desired as a catalytic agent to hasten the reaction. At the end of the refluxing operation the toluol is distilled oil. and the batch cooled and treated to eflect a separation of the unoxidized and nonhardening oil constituents. This is accomplished bytreating the batch with 3 to 4 volumes of petroleum naphtha (boiling range to 160 0.).

The unoxidized and non-hardening oil constituents, together with any remaining uncombined fatty acids dissolve in the extracting solvent to form an upper layer. The highly oxidized oil constituents, viz., the oxidized glycerides of linoleic and linolenic acids, combined with the free fatty acids form a lower layer. The upper layer is removed by decantation. The extraction process is preferably repeated two or three times to insure an adequate separation. The remaining portion comprising the reaction products of the fatty acids and the oxidized glycerides of linoleic and linolenic acids is then subjected to low heat and preferably at reduced pressure to remove the last portions of the extracting solvent. The resin-like reaction product,either in solution or freed of solvent, constitutes another embodiment of our product invention and for convenience in subsequent handling may be dissolved in a suitable solvent such as toluol, xylene, ethyl alcohol, or other similar coating solvent.

Method III The third method comprises the-steps of admixing with a rying or semi-drying oil a substantial amount of fatty acids selected from the group specified, subjecting the mixture to oxidation limited to the formation of uncoagulated products of oxidation, and separating from the reaction products a substantial proportion of the unoxidized and non-hardening oil constituents thereof.

Example-To 12 parts of linseed oil is added one part of the free fatty acids of linseed oil and the mixture is heated to about 80 C. A suitable drier, for example .04% cobalt linoleate, is added. The batch is then vigorously blown with air for, a period of 10 to 25 hours. When a tested sample Just fails to completely dissolve in ethyl ether, oxidation is discontinued. The batch is transferred from the oxidizer to a' tank fltted'with an agitator. It is then treated with 3 to 4 volumes of petroleum ether (boiling range 30 to 75 C.). The unoxidized and non-hardening oil constituents and any remaining uncombined fatty acids dissolve in the extracting solvent to form an upper layer. The oxidized glycerides of linoleic and linolenic acids combined with'the linseed oil fatty acids form a. lower layer. The upper layer is removed by decantation and the extraction process repeated two or three times to assure adequate separation, the balance of the extracting solvent being. removed by low heat. The remaining portion comprises chiefly the reaction products of the highly oxidized glycerides of linoleic and linolenic acids with the linoleic and linolenic fatty acids. It may also comprise a small proportion of-highly oxidized fatty acid complexes, that is, fatty acids (linoleic and linolenic) which have becomeoxidized and then reacted with additional free fatty acid to form a resin-like substance. These reaction products, with or without the presence of such fatty acid complexes, constitute an embodiment 'of our product invention. For convenience'in handling 'linoleic and linolenic acids 3 they may be dissolved in toluol, ethyl alcohol, butyl alcohol, or similar coating solvent. a

It is to be noted that in each method the oxidation of the drying or semi-drying oil is discontinued at or just before the point where the constituents of the oxidized oil or the reaction products thereof with the fatty acids commence to coagulate to the gel or linoxyn phase. This point may be determined by the ethyl ether test. As long as no linoxyn is formed the constituents of theoil undergoing oxidation will dissolve completely in ethyl ether, but upon the formation of linoxyn a Jelly-like precipitate will appear in the sample tested. Following the deresin-like products varies from 60% to based practicing our process invention according to Method I or vII, the percentage yield of those desired oxidized constituents of the oil may be somewhat increased by adding to the oil, prior to oxidation, a small amount-.1% to 2.0%--of maleic acid (or maleic acid anhydride) or equivalent acidic substance difllcultly volatile at a processing temperature.

v'I'he desired oxidized oil constituents which constitute the oil base in the preparation of the resin-like product of our invention are constituents which are soluble in ethylether, but insoluble in petroleum ether, and comprise chiefly the oxidized glycerides of linoleic and linolenic acids in fluid and uncoagulated phase. The unoxidized oil constituents in the oxidizing treatment and are removed in either constituents of the property of hardening, but were not so converted, such as the glycerides of linoleic and completion of the oxidizing treatment which'are removed to a substantial extent bythe separation treatment above-described. Furthermore, as noted in the particular descriptionof Methods II and III, the separation treatment when conducted subsequent acids and the oxidized oil constituents, removes any uncombined fatty acids remaining after completion of the refluxing operation.

The products of our invention are substances of a resin-like nature and of high molecular weight. Although the invention is not predicated upon any particular theories we believe that the following chemical reactions may occur. I 1

'The oxidation of the long chain unsaturated fatty acid glycerides such as the glycerides of and semi-drying oils produces keto' and hydroxy groups at the points of unsaturation, i. e., where the double bonds occur in the carbon chain.

which are not oxidized to the interaction of the fatty to the above-mentioned iected fatty acidmay become original point of As is first formed, thus:-

iii Y e These peroxide groups selves into one or both of the following forms A CIB!I: r

n o -c-t- 445. ii oi 3-3) \--C==C- (8 oil 01!:

'It is with these keto and hvdroxy groups"A and "B" that the long chainfatty acids, of '14 to 22 carbon atoms are caused'to react. The attachment of the fatty acid with the splitting of! of water may occur as follows, taking linoleic acid as an illustrative example: 1

Considering that each molecule of the glyceride of either linoleic or linolenic acid contains three fatty acid radicals. and therefore six or double bonds rcnine unsaturatedpgroups or spectively and that after oxidation, keto and hydroxy groups at these points of unsaturation, are to three molecules of the seattached ateach unsaturation or double bond. It will readily be seen thatreaction products of very high molecular weight will be formed. It is these products, comprising the fluid oxidized glycerides of linoleic or linolenic acids resulting from the oxidation of a drying or semidrying oil and with which are united one or more fatty acid chains of '14 to 22 carbon atoms and from which reaction products a substantialproportion of the petroleum ether soluble constituents have been separated, which constitute the embodiment of our product invention.

Although it is, desirable that the amount of unoxidizedand non-hardening oil constituents remaining admixedwith the ultimate reaction products should be at a minimum, nevertheless, the diflicuity of securing, in-commercial operation a quantitative elimination ofv these conattempt to oxidized oil products, or from the reaction products resulting from the interaction of the fatty acids with such oxidized oil products, of a substantial proportion of the unoxidized and nonhardening oil constituents. The properties and advantages characte i i s the products of our invention may be realized and enjoyed it the separation of the undesirable constituents of the oxidized oil. from .the desired oxidized oil constituents or from the reaction products of w 9,040,401 a result of the oxidation a peroxide groupthen rearrange them-- stituents. offsuch on. and

the oxidized oil and fatty acids isicarried'to' suchan extentthat theultimate reaction products contain but approximately 10% or less ofv such undesirabl'eoil constituents, i. uent's soluble in petroleumether. V

inaccordance with the above disclosure-.. novel productsiof our; invention-exhibit highly desirable properties particularly adapted for use as or. in vehicles for enamels, paints, varnishes, lacque or. other protective coating compositions, or as or inibinders for mouldable composition such as linoleum. The reaction products obtained by interaction of the oxidized glycerides of linoleic or linolenic acids of oxidized drying or se -dryingoil with fatty acids of the unsaturated series of 14 to 22 carbon atoms and separated from a substantial proportion of the'unoxidiz'ed and non-hardening oil constituents, impart to protective coating compositions improved gloss, improved adhesion and increased toughness. Such reaction products also possess the property of fast dryi or setting upon evaporation of thecoating solvent, 7 and do not require further oxidation to harden as is usual with drying orse -dryingoil products. The reaction products action of the oxidized glycerides of linoleic or linolenic acids of oxidized drying or semi-drying oil with fatty acids ofthe saturated-series of 14 to 22 carbon atoms and separated from a substantial proportion of the unoxidized and non-hardening oil constituents, impart to protective coating compositions both improved gloss and improved adhesion and are particularly adapted for use in conjunction'withcellulose ester vehicles. when so used they retard the otherwise too rapid setting of impart to the protective coating a markedly improved and permanent flexibility.

It should be clear from the foregoing description that the advantages of our invention reside in the discovery and development of certain new resinlike substances prepared drying oils and fattyacids by limited oxidation of the dryingor semi-drying oil, reaction of selected longchain fatty acids with certain oxidized conthe separation of specified undesirable non-hardening constituents of the oxidized oil either before or after the'interaction of the desired oxidized oil constituents and fatty acids, whereby the ultimate resinous} reaction products contain less than about 10% of constituents soluble in petroleum, ether. It is ,apparentthat the teachings of this invention may be applied in many ways and that thelnovel products will find wide and varied use.

We claim: I

l..The,process which comprises the steps of subjecting a substance comprising a drying or semi-drying. oil to oxidizing treatment limited substantially to the formation ofuncoagulated products of oxidation, effecting interaction of a fatty acid "characterized by 14 to 22 carbon atoms,

tion of the oxidized oil,'-treating theoxidized oil to remove therefrom unoxidized oil constituents and non-hardening oil constituents,

the vehicle and and effecting obtained by interfrom drying or semi- I interaction of the remaining oxidized glyceride constituents of the oxidized oil with a'fatty' acid characterized by 14 to 22 carbon atoms.

3. The process which comprises the steps of subjecting a substance comprising a drying or semidrying oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, effecting interaction of oxidized glyceride constituents of the products of oxidation with a fatty acid characterized by,14 to 22'carbon atoms and present in an amount in excess of that normally present in the oil, and extracting with a. low boiling hydro-carbon.

4. The process which comprises the steps of subjecting a substance comprising a drying or semidrying oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, extracting the resulting products with a low boiling hydro-carbon to remove therefrom unoxidized and non-hardening oil constituents, and effecting interaction of oxidized glyceride constituents with a fatty acid characterized by 14 to 22 carbon atoms.

5. The process which comprises the steps of I subjecting a substance comprising a drying or semi-drying oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, and effecting interaction of a fatty acid characterized by 14 to 22 carbon atoms, in an amount in excess of the amount normally present in the oil, with oxidized glyceride constituents of the products of oxidation.

6. The process which comprises the steps of subjecting a substance comprising a drying or semidrying oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, refluxing with oxidized glyceride constituents of such products of oxidation 5% to 25% of a fatty acid characterized by 14 to 22 carbon atoms, and, by fractional extraction, removing unoxidized oil constituents and non-hardening oil constituents.

7. The process which comprises the steps of subjecting a substance comprising linseed oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, effecting interaction of a fatty acid characterized by 14 to 22 carbon atoms, in an amount in excess of the amount normally present in the oil, with oxidized glyceride constituents of the products of oxidation, and separating and removing unoxidized oil constituents and non-hardening oil constituents.

8. The process which comprises the steps of subjecting a substance comprising a drying or semidrying oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation in the presence of a fatty acid characterized by 14 to 22 carbon atoms, in an amount in excess of the amount normally present in the oil and thereby efiecting interaction of said fatty acid with oxidized constituents of said products of oxidation, and separating and removing unoxidized oil constituents and non-hardening oil constituents.

9. A composition comprising the reaction product of a fatty acid characterized by 14 to 22 carbon atoms and oxidized glyceride constituents resulting from oxidation of a drying or semi-drying oil, the amount of said fatty acid being in excess of the amount thereof normally present in said oil and said reaction product having associated with it less than 10% of unoxidized and nonhardening oil constituents soluble in petroleum 5 ether.

10. A composition comprising the reaction product of a fatty acid characterized by 14 to 22 carbon atoms and that component of oxidized drying or'semi-drying oil which .afteroxidation of the oil is in fluid phase, is separated from a substantial proportion of unoxidized and nonhardening' oil constituents of the oxidized oil, and is capable of hardening without further substantial oxidation.

11. A composition .comprising the reaction product of a fatty acid characterized by 14 to 22 carbonatoms and that-component of oxidized drying or semi-drying oil which after oxidation of the oil is in fluid phase, is separated from a substantial proportion of unoxidized and'nonhardening oil constituents of the oxidized oil, and is capable of hardening without further substantial oxidation, said composition having associated with it less than 10% of constituents soluble in petroleum ether. and being substantially identical with the product of the process of claim 1.

12. A composition comprising the reaction product of a fatty acid characterized by 14 to 22 carbon atoms and that component of oxidized linseed oil which after oxidation of the oil is in fluid phase, is separated from a substantial proportion of the unoxidized and non-hardening oil constituents, and is capable of hardening without further substantial oxidation.

13. A composition of matter comprising the reaction product of a fatty acid of 14 to 22 carbon atoms and an oxidized drying or semi-drying oil, the amount of said fatty acid being'in excess of the amount thereof normally present in said 011 and said reaction product having associated therewith less than 10% of constituents soluble in petroleum ether.

14. A composition of matter comprising the reaction product of a fatty acid of 14 to 22 carbon atoms and oxidized glycerides of linoleic and/or linolenic acids obtained by oxidation of a drying or semi-drying oil and separation therefrom of a substantial proportion of unoxidized and nonhardening-constituents of the oxidized oil.

15. A composition comprising the reaction product of a fatty acid characterized by 14 to 22 carbon atoms and liquid oxidized glyceride constituents resulting from oxidation of a drying or semi-dryingoil.

16. A composition of matter comprising the reaction product of a fatty acid of 14 to 22 carbon atoms and liquid oxidized glycerides oi linoieic and/or linolenic acids.

17. A composition comprising the reaction product ,of a drying'oil fatty acid characterized by 14 to 22 carbon atoms and oxidized glycerides of linoleic and/or linolenic acids obtained by oxidation of a drying or semi-drying oil and separation therefrom of a substantial proportion of unoxidized and non-hardening constituents of the oxidized oil.

18. The process which comprises the steps of subjecting a substance comprising a drying or semi-drying oil to oxidizing treatment limited substantially to the formation ofuncoagulated products of oxidation in the presence of a fatty acid characterized by 14 to 22 carbon atoms and present, in an amount in excess of the amount normally present in the oil and thereby effecting interaction of the fatty acid with oxidized glyceride constituents of said product of oxidation, and separating and removing unoxidized oil constituents and non-hardening oil constituents and uncombined fatty acid.

- oxidation with fatty.

' last-named treatment unoxidized oil 19. The process which comprises the steps of subjecting a substance comprising a drying or semi-drying oil to oxidizing treatment limited substantially to the formation of uncoagulated products of oxidation, treating the product of said acid characterized by 14 to 22 carbon atoms and thereby effecting interaction of the fatty acid with oxidized glyceride constituents of said products of oxidation, and separating and removing from the product of said constituents V treating the product of I and ,extracting'the 7 products of said last-named treatment with a low-boiling hydrocarbon.

21. A composition comprising the reaction product of that componentv of, oxidized drying or semi-drying oil which after oxidation of the oil is in fluid phase, is separated from a substantial proportion of unoxidized and non-hardening oil constituents of the-oxidized oil, and is capable of hardening without further substantial oxidation, and an excess, over the amount thereof normally present characterized by 14 to 22 carbon atoms.

22. A composition comprising the reaction product of liquid oxidized giyceride constituents resulting from oxidation of drying or semi-drying oil limited to the formation of liquid oxidized constituentsv and an excess of fatty acid,.over

the amount thereof. normally present in said oii,

tol22 carbon atoms. 4 ROBERT D. BONNEY. WALTER s. noon.

characterized by 14 in said oil, of fatty acid 

